Patent GB-1074233-A (GB)
Title: Cuprous chloride or bromide complexing agents
Inventor: LONG ROBERT BYRON
IPC: C07F1/00
Filed: 1964-06-19
Abstract: Cuprous chloride or bromide particles having a porosity of above 10% of the total volume of a particle as 550-10,000 <\>rA pores are prepared by the precipitation of the cuprous halide particles complexed with a complexing agent which forms a stable complex of ratio copper to complexing agent greater than 1:1 from (1) liquids containing the complexed cuprous halide in solution and (2) liquid mixtures of the complexing agents and an activating material selected from monoolefin solvents for the cuprous halide, alcohols, glycols, acids, water containing uncomplexed cuprous halide particles slurred therein, and dissociating the complexed cuprous halide particles to regenerate cuprous chloride or bromide.  Suitable complexing agents, gaseous or liquid, may be:  carbon monoxide, hydrogen cyanide, C2 to C16 compounds containing one or more of the following functional groups:-  (a) C=C, e.g. ethylene, propylene, butylene, isobutylene, pentenes.  Olefinic aromatic compounds may also be used, e.g. styrene.  (b) C=R=C, where R is C or an alkylene group, e.g. conjugated or non-conjugated aliphatic, cyclic or alicyclic diolefins or polyolefins such as allene, butadiene, isoprene, piperylene, octadienes, cyclohexadiene, cyclo-octadiene, divinyl benzene, cyclododecatriene.  (c) -C­C-, e.g. aliphatic or alicyclic acetylenes or acetylenes containing additional unsaturation, e.g. acetylene, methylacetylene, propyl acetylene, phenyl acetylene, vinyl acetylene. (d) -C­N, aliphatic or alicyclic saturated or unsaturated nitriles such as acetonitrile, acrylonitrile, propionitrile, phenylnitrile, methacrylonitrile, ethacrylonitrile, methane nitrile, ethane nitrile, propane nitrile.  Aryl, alkaryl, aryl-alkyl nitriles may also be used.  (e) C=O unsaturated carbonyl compounds, e.g. propenal, butenal, pentenal; unsaturated ketones, e.g. 1-butene-3-one, 1,4-pentadiene-3-one, 2 - pentene - 4 - pentadiene - 3 - one, 2 - pentene-4-one.  Pure streams, or streams diluted with an inert gas, or natural dilute petroleum streams (e.g. butadiene diluted with butene and butanes) can be used.  Reaction conditions are those within which the desired complex is stable, e.g. - 80-80 DEG  C., 1 to 165 p.s.i.a. pressure.  Suitable solvents in (1) may be aqueous concentrated or dilute inorganic acids, e.g. 2 to 12N HCl or HBr, and concentrated aqueous inorganic solutions. Particles above 10m  sizes are prepared by slow precipitation, e.g. <1000 gms./hour/litre. Slow precipitation may be by (a) addition of an antisolvent; (b) change in temperature, (c) evaporation of solvent; or by addition of the complexing agent with or without antisolvent to an uncomplexed cuprous halide solution in a solvent having lower solubility for the complex. Antisolvents may be water, C1 to C10 alcohols, e.g. methanol, ethanol, isopropanol; water-soluble ethers, esters, ketones, e.g. diethyl ether, acetone, methyl ethyl ketone, methyl acetate; sodium hydroxide solution.  Precipitation may also be from an uncomplexed solution of cupric chloride or bromide by adding a complexing agent and a reducing agent, e.g. SO2 or Na2SO3.  Suitable activating agents in (2) may be C1 to C10 monoalcohols, e.g. methyl, ethyl and n-propyl; C1 to C10 glycols, e.g. ethylene and propylene glycol; C4 to C8 branched or straight chain olefine, e.g. butene-1, isobutylene, pentene-1, hexene-1.  The cuprous halide may be above 50% 10-600m  single particles or spherical macroparticles composed of continuously joined 5m  microparticles.  The particles form especially active, complexing agents in the separation of compounds capable of forming a complex with cuprous chloride or cuprous bromide, e.g. in the fluid bed recovery of butadiene from crude butadiene, ethylene separated from steam cracking a C2 stream, acrylonitrile from acetonitrile, carbon monoxide from hydrogen, allene from methyl acetylene, piperlenes from cyclopentene. Preferred complexing and decomplexing conditions in these separation processes are specified.ALSO:Cuprous chloride or bromide particles having a porosity of above 10% of the total volume of a particle as 550-10,000 DEG  A. pores are prepared by the precipitation of the cuprous halide particles complexed with a complexing agent which forms a stable complex of ratio copper to complexing agent greater than 1 : 1 from (1) liquids containing the complexed cuprous halide in solution and (2) liquid mixtures of the complexing agents and an activating material selected from monoolefine solvents for the cuprous halide, alcohols, glycols, acids, water containing uncomplexed cuprous halide particles slurred therein, and dissociating the complexed cuprous halide particles to regenerate cuprous chloride or bromide.  Suitable complexing agents, gaseous or liquid, may be:  carbon monoxide, hydrogen cyanide, C2 to C16 compounds containing one or more of the following functional groups. (a) C = C, e.g. ethylene, propylene, butylene, isobutylene, pentenes. Olefinic aromatic compounds may also be used, e.g. styrene.  (b) C = R = C, where R is C or an alkylene group, e.g. conjugated or non-conjugated aliphatic, cyclic or alicyclic diolefines or polyolefines such as allene, butadiene, isoprene, piperylene, octadienes, cyclohexadiene, cyclooctadiene, divinyl benzene, cyclododecatriene.  (c) -C­C-, e.g. aliphatic or alicyclic acetylenes or acetylenes containing additional unsaturation, e.g. acetylene, methylacetylene, propyl acetylene, phenyl acetylene, vinyl acetylene. (d) -C­N, aliphatic or alicyclic saturated or unsaturated nitriles such as acetonitrile, acrylonitrile, proprionitrile, phenylnitrile, methacrylonitrile ethacrylonitrile, methane nitrile, ethane nitrile, propane nitrile.  Aryl, alkaryl, arylalkyl nitriles may also be used. (e) C = O unsaturated carbonyl compounds, e.g. propenal, butenal, pentenal; unsaturated ketones, e.g. 1-butene-3-one, 1,4-pentadiene-3-one, 2 - pentene - 4 - pentadiene - 3 - one, 2 - pentene-4-one.  Pure streams, or streams diluted with an inert gas, or natural dilute petroleum streams (e.g. butadiene diluted with butene and butanes) can be used.  Reaction conditions are those within which the desired complex is stable, e.g. - 80-80 DEG  C., 1 to 165 p.s.i.a. pressure.  Suitable solvents in (1) may be aqueous concentrated or dilute inorganic acids, e.g. 2 to 12 N -HCl or HBr, and concentrated aqueous inorganic solutions. Particles above 10 m Pl sizes are prepared by slow precipitation, e.g. <1000 gms./ hour/lite.  Slow precipitation may be by (a) addition of an antisolvent, (b) change in temperature, (c) evaporation of solvent; or by addition of the complexing agent with or without antisolvent to an uncomplexed cuprous halide solution in a solvent having lower solubility for the complex.  Antisolvents may be water, C1 to C10 alcohols, e.g. methanol, ethanol, isopropanol; water soluble ethers, esters, ketones, e.g. diethyl ether, acetone, methyl ethyl ketone, methyl acetate; sodium hydroxide solution.  Precipitation may also be from an uncomplexed solution of cupric chloride or bromide by adding a complexing agent and a reducing agent, e.g. SO2 or Na2SO3. Suitable activating agents in (2) may be C1 to C10 monoalcohols, e.g. methyl, ethyl and n-propyl; C1 to C10 glycols, e.g. ethylene and propylene glycol; C4 to C8 branched or straight chain define, e.g. butene-1, isobutylene, pentene-1, hexene-1. The cuprous halide may be above 50% 10-600 m  single particles or spherical macroparticles composed of continuously joined 5 m  microparticles.  The particles form especially active, complexing agents in the separation of compounds capable of forming a complex with curpous chloride or cuprous bromide, e.g. in the fluid bed recovery of butadiene from crude butadiene, ethylene separated from steam cracking a C2 stream, acrylonitrile from acetonitrile, carbon monoxide from hydrogen, allene from methyl acetylene, piperylenes from cyclopentene. Preferred complexing and decomplexing conditions in these separation processes are specified.